
Citation: | Yiming Ma, Weimin Ruan, Chao Niu, Tianshui Yang. Movement History of the Microcontinents from the Tibetan Plateau Based on Paleomagnetic Results with Sufficient Sampling Units. Journal of Earth Science, 2022, 33(5): 1072-1080. doi: 10.1007/s12583-022-1721-2 |
Paleomagnetic results cannot be applied in global and regional tectonic reconstructions unless the paleosecular variation has been adequately averaged. However, how many sampling sites and samples are enough to calculate a reliable paleopole remains debated. Based on the relation among the sampling sites
Coesite is the high-pressure polymorph of quartz that has the same composition as SiO2. But coesite has larger density than that of quartz. The initial temperature and pressure condition of formation of coesite is 600 ℃-800 ℃ and 2.4-2.8 GPa. The coesite was for the first time synthesized by Coes in 1953 at high temperature and pressure (Coes, 1953). Coesite was firstly discovered as inclusions in clinopyroxene and garnet in high-grade pelitic blueschist from Dora Maira massif of western Alps and in dolomite eclogite from Caledonides of west Norway respectively by Chopin (1984) and Smith (1984). And coesite has subsequently been reported in the eclogite of Dabie Mountains (Okay et al., 1989; Wang et al., 1989; Xu, 1987). This implies that the crustal rocks of lower density had ever been subducted to the depth of more than 90 km where there lies the upper mantle of higher density during continental collision, and then were exhumated to the surface with fast speed. Consequently, the coesite has been widely considered as the typical mineral representing ultrahigh pressure metamorphism (Cong and Wang, 2000).
Dabie Mountains (hereinafter as Dabie) is the east extension of Qinling-Tongbai orogenic belt, which is segmented by Tanlu fault at the east segment. It is located between North China block and Yangtze block and has complex history of structural evolution. The ultrahigh pressure metamorphism in Dabie has become the focus for geologists since coesite-bearing and diamond-bearing eclogites have been discovered from these old metamorphic rocks (Xu et al., 1992; Okay et al., 1989). However, coesite and diamond as the indicators of ultrahigh pressure metamorphism was only reported from southern Dabie where ultrahigh pressure rocks are well outcropped, and coesite-bearing eclogites have not been found in northern Dabie (Cong and Wang, 1999; Wang and Cong, 1996; Zhang et al., 1996; Zhai et al., 1994). Eclogites without coesite and retrograded eclogites have been found in northern Dabie by Liu et al. (1999), Xu et al. (1999) and Wei et al. (1997). Geologists thus always pay attention to whether northern Dabie has also experienced ultrahigh pressure metamorphism. Quartz exsolution has been reported in clinopyroxene from eclogite of several locations (Dobrzhinetskaya et al., 2002; Su et al., 2001; Katayama et al., 2000; Tsai and Liou, 2000; Bakun-czubarow, 1992; Smith, 1984). Some scholars think that the early clinopyroxene contained Ca-Eskola composition or silica-rich component which were stable at p≥2.5 GPa and t=927℃, and that SiO2exsolved as orientated needles due to pressure decreases. Therefore, this exsolution texture can be regarded as evidence that the protolith has experienced ultrahigh pressure metamorphism. Quartz exsolution has also been found in clinopyroxene in high-pressure granulite from Münchberg massif, Germany and in ultrahigh pressure eclogite from Kokchetav massif respectively (Katayama et al., 2000; Gayk et al., 1995). Gayk et al. (1995) and Katayama et al. (2000) calculated that the preexisting supersilicic clinopyroxene contains 10 mol% of the Ca-Eskola component and suggested that this component become unstable with pressure decrease, resulting in exsolution of quartz rods in the matrix clinopyroxene. Tsai and Liou (2000) and Su et al. (2001) suggested needle-shape quartz as the indicator of ultrahigh pressure metamorphism of protolith and confirmed that ultrahigh pressure eclogites also exist in north Dabie. Hereby, a detailed investigation on coesite inclusion and quartz exsolution in eclogite has an important theoretical significance for structural deformation and metamorphism history of Dabie.
The purpose of this paper is to (1) compare systemically the Raman spectrum in transformation from coesite to quartz; (2) investigate the characteristics of Raman spectrum of silica exsolution in omphacite from eclogite and topological relationship between the long axis of silica exsolution and lattice orientation of omphacite using Raman spectroscopy and U-stage, and (3) discuss whether silica exsolution may be taken as the indicator of ultrahigh pressure metamorphism or not.
The samples studied here are from two regions.
(1) Eclogites in southern Dabie Mountains. HHW-1, SM-3, GH-4 and RP-28 are representative eclogite samples from Huanghuawu, Shima, Ganghe and Shuanghe respectively. Eclogites are pale-green in color, with medium to coarse equigranular texture and relative significantly foliated. The eclogite consists of garnet (c. 45 %-50 % volume fraction) and omphacite (c. 40 %-50 % volume fraction) together with minor amounts of quartz, rutile and phengite. Raman spectrum experiments on coesite inclusions are operated in the first three coesite-bearing eclogite samples. Coesite inclusion is characterized by relative higher relief and lower interference color than that of quartz and associated radial fracturing of the host mineral under microscope. Coesite relic inclusions in garnet and/or omphacite from eclogite in Dabie are shown in Fig. 1. This figure shows that coesites with higher relief are rimmed by quartz pseudomorph after coesite. These coesite inclusions are 10-50 μm in size and 30 μm in average. In eclogite sample RP-28 from Shuanghe orientated silica exsolutions are presented in omphacite and coesite inclusion is not found.
(2) Eclogites from Alpe Arami in Switzerland. Sample A99was collected from ultrahigh pressure rocks of garnetlherzolite in Alpe Arami, Switzerland. The garnets exhibited abundant exsolved needles of rutile and small, oriented and euhedra-l to-subhedral crystals of pargasite-edenite amphibole, which were always accompanied by an orthopyroxenespinel symplectite and were usually accompanied by magnesite, apatite and an Fe-Ni sulfide. The clinopyroxenes commonly display bright apple-green colors, present both as inclusions in garnet and as clusters around the margins of garnets (Dobrzhinetskaya et al., 1996). In this sample, garnet is 2.4 cm×1. 5 cm in size with a diopside inclusion (0.5 cm×1.1 cm in size) inside, and wel-l developed orientated silica rods are present in the diopside inclusion (Fig. 2d).
Laser Raman spectrum (LRM) is a kind of associated scatter spectrum and it also provides information on molecule (not element) component and molecule ligand structure. As a complementary technique of infrared spectrum, it not only offers information of molecule radical structural unit and ligand symmetry, but also is sensitive to fine structure of mineral such as ordered-disordered occupation of ions and defects. Therefore, LRM is called as "fingerprint spectrum", which makes it possible for one exclusive spectrum corresponding to one substance and be used to distinguish polymorphic substances (such as coesite and quartz). Above all, this technique does not damage the samples, and double polished thin sections are enough for observation and examination. Thereby, it has been an apotheosis to identify coesite, diamond and aragonite by using of LRM technique in the study of petrology. LRM has been a new non-destructive in situ micro-area analytic method in earth science since 1970s. However, since the beginning of 1980s, mineralogists in China have started to pay attention to the work in this area. Xu et al. (1992) and Xu and Li (1996) began to study coesite using LRM firstly.
Spectra were obtained with a Renishaw RM-1000system equipped with a microscope stage in the open research laboratory of China University of Geosciences. Excitation was provided by the514. 5nm line of an Argon-ion laser at 3. 4 mW, focused to a spot size of 1.5 μm. Spectra were measured with spectrometer entrance slits at 12.5 μm. All the analyzed samples are conventional double polished thin sections. The Raman spectroscopy characters of silica exsolution and transformation from coesite to quartz were studied.
Studies of mineral inclusions in metamorphic minerals often provide qualitative and quantitative information about the reaction and growth history of a particular metamorphic terrane as the relict inclusion assemblage records an earlier stage of the metamorphic history, and is preserved by virtue of being surrounded by the porphyroblast (Tabata et al., 1998). Therefore, for the study of ultrahigh-pressure metamorphic terranes, armored relict within host minerals plays a particularly important role in deciphering the metamorphic record prior to the formation of the matrix assemblage. 521 cm-1 is the dominant Raman shift of coesite in relic inclusion assemblage of coesite and quartz, and 464 cm-1 is the dominant Raman shift of quartz (Parkinson, 2000; Parkinson and Katayama, 1999; Boyer et al., 1985). 45points of Raman spectrum were obtained from the center to the rim of several coesite inclusions. The coesite inclusion in garnet from eclogite of Ganghe, southern Dabie is shown in Fig. 2. Experiments were carried out on a profile in the relic assemblage from coesite relic center to its rim, then the border of coesite and quartz pseudomorph after coesite, and at last the quartz pseudomorph. Representative point Nos. 1, 4, 5are selected to explain here. The systemic experimental results show that in the core of coesite the Raman peaks of coesite and quartz coexist, but the Raman peak of 521 cm-1of coesite (521 cm-1, 277 cm-1, 177 cm-1, 152 cm-1) occupies a dominant position. While along with the measurement to the rim of test points, the Raman peaks of coesite weaken gradually and eventually dissappear at the measured positions of quartz pseudomorph after coesite. On the contrary, the Raman peak of quartz (464 cm-1) is enhanced gradually to the strongest. Noticeably, the characteristic Raman peak of coesite occurs at the position of phase-transformed quartz (Fig. 2c). This phenomenon has repeatability in the wel-l preserved inclusion of relict coesite assemblages.
Strongly oriented silica exsolutions occur as needles or rods within omphacite under observation of optical microscope and are 20-50 μm in length and 2-3 μm in width. They usually are present in the core of omphacites and align subparallel to the cleavage of omphacites (Fig. 3). In the omphacites with silica exsolution, the proportion of silica can occupy up to 10%-30% area of host crystals.
That the characteristic Raman peak of coesite and quartz coexist in the spectrogram of phase-transformed quartz was detected in the process of Raman experiments from core to the rim of relict coesite inclusions. Further Raman experiments were made on the exsolved silica in omphacite of eclogite from southern Dabie of Central China to try to analogically find out if characteristic Raman peak of coesite appears in the Raman spectrogram of silica. Preliminary study of 13 measured points on 7 quartz exsolutions shows that only the characteristic peak of quartz (464 cm-1) and clinopyroxene (352 cm-1) occurs in the Raman spectrogram without the characteristic Raman peak of coesite (Fig. 4).
Raman spectrocopy study was made on quartz vein that crosscuts the UHP eclogite in Wumiao, southern Dabie. The quartz vein is later than eclogite body according to the field observations. Raman spectrograms of silica exsolution in clinopyroxene of eclogite from Alpe Arami and southern Dabie area were also analyzed to make comparison with the Raman spectrum of quartz vein. Results show that the Raman spectrograms of these three samples are similar that only the characteristic Raman peak of quartz is presented, and the coesite peak is not presented (Fig. 5).
In order to find out the topological relationship between the long axis of quartz exsolutions and lattice orientation of omphacite, measurements of the long axis of 80quartz exsolutions in 12omphacite grains were made in eclogite (RP-28) from Shuanghe in southern Dabie by using of U-stage. The measurements were projected in Fig. 6. In Fig. 6, cryst allographic axis a, b and c of omphacite were chosen as the reference coordinate axes, which correspond to the [100], [010], [001] lattice orientations of omphacite respectively. Results show that the long axis of quartz exsolution aligns approximately in two directions: one is parallel to the (100) rifting plane, and the other is subparallel to the (-101) plane.
The characteristic Raman peaks of coesite and quartz can occur both at the positions of phase-transformed quartz and coesite. From the variety of intensity, the Raman peak of coesite weakens gradually from coesite centre to its brim, while the Raman peak of quartz strengthens correspondingly. This implies that micro-crystals of quartz, early production of phase transformation, might exist in coesite and the transformation is a continuous process. According to experimental study of phase transformation rate (Zhang and Jin, 1999; Mosenfelder and Bohlen, 1997), the garnet can support high inner pressure and coesite inclusion be preserved because of this reason during decompression, which accounts for fast exhumation rate and weak influence of later water. If the water fugacity is increased, it will accelerate the phase transformation from coesite to quartz that makes it harder for coesite to preserve.
The only characteristic peak of quartz and weak mixing peak of quartz-coesite occurs in the Raman spectrogram of quartz exsolution in omphacite of eclogite. The same characteristics are presented in Raman spectrum of later quartz vein. Topological relationship study between the long axis of quartz exsolutions and lattice orientation of omphacite shows that quartz exsolution aligns approximately in two directions: one is parallel to the (100) parting plane, and the other is subparallel to the (-101) plane. Two possible explanations of above-mentioned phenomenon are the following as: (1) Original exsolution was coesite, but coesite was completely transformed into quartz during exhumation because they exsolved along parting plane or cleavage, which is normally the weak orientation of stress in crystallization. Recently Zhang Junfeng (Geology Department, University of California (Riverside), personal communication, 2002) discovered that SiO2 exsolution occurs in omphacite in condition of 3 GPa and 1200K. (2) Only quartz exsolution appears in omphacite as SiO2exsolved under stable field of quartz.
Northern Dabie has always been considered to be a region where the terrane did not experience ultrahigh pressure metamorphism because coesite-bearing eclogite has not been found. Recently, SiO2exsolution in clinopyroxene of eclogite and garnet-pyroxenite were found respectively (Su et al., 2001; Tsai and Liou, 2000). The same phenomenon was found by Zhang et al. (2001) in UHP metamorphosed eclogite from western Tianshan of Xinjiang. They take the exsolution texture as one indicator of the UHP metamorphism. Their speculations are based on former research theory (Katayama et al., 2000; Angel et al., 1988): the incorporation of excess silica in sodium rich pyroxene could stabilize the pyroxene and expand its stability field to higher pressure, and exsolution of SiO2rods were produced with the decreasing of pressure. Therefore, Ca-Eskola component in the peak metamorphic clinopyroxene broke down by a retrograde reaction: 2Ca0.5□0.5→AlSi2O6→CaAl2SiO6+3SiO2 resulting in exsolution of the quartz rods. Accordingly, the theory and the reaction indicate that the Ca-Eskola clinopyroxenes are formed in subducted crustal or supercrustal rocks at high pressures and temperatures. The vacancy-containing clinopyroxene may have an important bearing on the physico-chemical properties of the subducted slab at upper mantle depth (Katayama et al., 2000). Up to the present, there is no direct experimental evidence that explains p-t condition of formation of silica exsolution rods exsolved from clinopyroxene, prior to or after peak metamorphism. For instance, the experiments done by Mao (1971) indicate that under 4 GPa and 1100-1700 ℃ jade-Ca Tschermak clinopyroxene can at least dissolve 7.5% excess SiO2, and this component of SiO2 can be enhanced with the increasing of pressure. Khankhova and Zharikov (1976) once made an experimental study of the system CaMgSi2O6-CaAl2SiO6-SiO2 at 3.5 GPa and 1200 ℃. The products of their subsolidus phase are clinopyroxene, garnet and coesite (or quartz), and excess silica is presented in the solid solution. Recently, Dobrzhinetskaya et al. (1996) considered quartz exsolution in clinopyroxene from eclogite of Alpe Arami was formed at peak metamorphism according to Fe2+-Mg exchange thermometer of garnet-clinopyroxene and calculations of equilibria with thermodynamic data. Zhu and Ogasawara (2002) suggested that the exsolution of phlogopite and coesite/quartz from super-silicic clinopyroxene in dolomite marble of the Kokchetav massif, northern Kazakhstan is formed at pressures of 8 GPa (1000 ℃). However, all those results are still difficult to answer these following questions: (1) How much is the critical content of excess SiO2 when formation of exsolution started? (2) What is the initial exsolution of SiO2? Is it just the quartz or the coesite, which is transformed into quartz under successive low-pressure condition? (3) What is the topological relationship between coesite/quartz and their host mineral clinopyroxene? Accordingly, further experiments are needed to prove that the quartz exsolution in eclogites can be considered as the evidence of ultrahigh pressure metamorphism. The authors consider that further experimental study at high pressure and temperature should be enhanced on the study of exsolution mechanism of supe-r silicate clinopyroxene, which could provide final experimental evidence on quartz exsolution as UHP indicator.
We thank Professor Jin Shuyan for helping in teaching measurements of quartz exsolution with U-stage. Many appreciations are to Dr. Dobrzhinetskaya L F of California University (Riverside) for constructive discussions on mechanism of quartz exsolution.
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